Vat dyestuffs of the anthrimide carbazole type



Patented Sept. 18, 1945 Glen M. Smyth, Plainfield, N, J., assignor toAmerican Cyanamid Company, NewYork, N. Y.,

a corporation of Maine No Drawing. Application October 16 194 3,

Serial No. 506,571. 1

4 Claims. (01. 2-6 s-16) This invention relates to vat dyestuffs of thepentanthrimide carbazole type and more particularly such dyestuffsderived from a new kind of pentanthrimides.

The new pentanthrimides which are used in preparing the carbazole vatdyestuffs of the present invention may,-be represented by the followingformula:

in which one X stands for hydrogen and. the:

other-X stands for'the radical:

Depending on which X standsfor the anthrirnide radical, the vatdyestuffs of the present invention may be represented the following Bothdyes dye cotton a, brown vat. They have excellent fastness to washing,perspiration and water-spotting, and

very good fastness to light and chlorine. Thedyes also have a veryimportant propertyof changing but little in shade on drying.- It is thuspossible for the dyer to judge the shade in the wet stage with greaterease and the dyeing operation may be speeded up and shade controlimproved thereby. t

The new dyestuffs are cold dyes but may also be used for printing. It isan advantage of the new dyestufis that they vat readily, the vatting yconditions not being critical as to amounts of by formulae agreenish-olive drab fromchlorbenzene,. to reaction temperature and thenadd in portions a mixture of the pentanthrimide and sodium carbonate.

The sodium carbonate; 5 may be replaced by other acid binding agentssuch as other alkali metal carbonates. The dyest'uffi'i then isolated byadding caustic alkali, steam strippin off the solvent and filtering. Thepreferred process referred to above is not claimed; generally for ringclosure of anthrimide compounds, that iorming the subject matter of acopending application of Smyth and Cullinam- Serial No. 506,572, filedOctober 16, 1943. Its use is claimed in the present application only inconnection with the production, of, the new pentanthrimide vat dyestufisof the present invention. The dyestufis of the present invention may bereadily acid pasted and if desired purified by customary acid pastingand oxidation methods.

As will appear from the description below of the preparation of the newpentanthrimides and from the examples, mixtures of isomericpentanthrimides are often obtained unless pure and more expensive rawmaterials are used. Fortunately' the two isomeric pentanthrimidecarbazoles of the present invention are so similar in shade andpractically identical in their other characteristics that mixtures maybe used without adverse results and withoutintroducing great difficultyin shade matching. This is a, very important advantage becausethelargest field of utility of dyestuffs of the present invention lies.in. low cost fabrics where the cost of the dyestufi usediis an extremelyimportant practical feature.

The pentanthrimides. are in general prepared by starting with a5"-'nitro an'thraquinone-l-sodium sulfonate or the corresponding 8-nitroisomer, or mixtures of, the two which are obtained when anthraquinonealpha-sulfonic-acid is nitrated with mixed acids. Separation of .the 1,5isomer from thenitration mixture easy as most of the 1,5 isomerseparates out and may be filtered off, but it is more diificult toobtain the 1,8 isomer in pure form. 1,8 isomer mixed with some 1,5 andother isomers satisfactory for 'the purpose of this invention may beobtained in good yield by diluting the filtrate mother liquor with waterto 80% sulfuric acid concentration. For most purposes it is notnecessary to use a chemically pure compound, although it results.

The flexibility with regard to raw materials used is a very importantfactor in producing the new pentanthrimid-es which inturnare'transformed into the carbazole dyestufis of the present givesthesame excellent comes a by-product which can be. obtained verycheaply. On the other hand, if the demand for nitroanthraquinonesulfonic. acids fordyestufis 0? the present invention is greater thanthe amount of 1,8 isomer which can be obtained as a by-product, anydesired proportion of the two may be used.

The next step regardless of the isomer used is to replace the sulfonicgroup by a chlorine atom. This procedure is effected in the conventionalmanner by heating with dilute hydrochloric acid and a chlorate. Thecorresponding nitro alphachloroanthraquinone is obtained and is thencondensed with alpha amino anthraquinone, preferablyin solutionv inboiling nitrobenzene using a cupriferous catalyst and, an acid bindingsubstance such as an alkali metal carbonate or acetate to unite with thehydrochloric acid set free. This reaction results in the production ofeither a 5on8 nitro-1,l-dianthrimide having the following formula:

Where one X stands forhydrogen and the other X for the nitro group.

The next step is nitration with mixed acid containing boric acid. Thetwo ni-tro groups presumably enter the 4 and 4' positions which are themost active hydrogens in the molecule. For best results it is desirableto usev an excess of nitric acid and this may result insomenitration oroxidation of the 2 or 2 position. Such reactions, however, areimmaterial because in the final synthesis of the carbazoles these twopositions are connected by the ring closure in any event.

The trinitro or higher nitrated compound produced by the above describednitration is then reduced to the triamino compound (possibly mixed withsome p-hydroxy compound), preferably using an alkali metal sulfide asthe reducing agent. The resulting compound which is probably either4',4,5-triamino-l,l'-dianthrimide or 4',4,8-triamino-1,1"-dianthrimideis reacted with 3 molecules of alphachlor anthraquinone, preferably byheating in nitrobenzene in the presence of a cupriferous catalyst withan acid binding agent such as an alkali metal carbonate or acetate. Thisgives the desired pentanthrimide. If desired, a substitutedalphachloranthraquinone such as 5-nitro-l-chloranthraquinone may be usedto produce a substituted pentanthrimide.

The invention will be described in greater detail in the followingexamples, but is not limited to the details therein set by weight.

forth. The, parts are EXAMPLE 8-nitro-1,1 -dia1 ithrimide 35 parts of8-nitro-l-chloroanthraquinone (made from anthraquinone-S-nitro-l-sodiumsulfonate by boiling with dilute hydrochloric acid and sodium chlorate)parts alpha amino an thraquinone, 5 parts cupric chloride crystals and48 parts soda ash are slurried in 400 parts of nitrobenzene. The mixtureis heated .to the boil, allowing the water formed by the reaction todistill. off, Aftera short time the brown colored mass turns adeep redcolor which is characteristic of the.8-nitr0-1,1 -dianthrimide. Thereaction is held at the boil for 2-5 hours. On cooling the8-nitro-1,1'-dianthrimide crystallizes out as a thick mass and can beisolated in sufiicient purity by diluting the slurry with 3-4 volumes ofethanol or methanol, in which the 8-nitro-1,1- dianthrimide isinsoluble,filtering and washing with alcohol to remove the mother liquor. The sodaash is then removed by slurrying the cake in dilute hydrochloric acid,filtering, and washing acid free. A nearly theoretical yield of drycrude product is obtained in this manner. An 80% yield of slightly purerproduct can be obtained by filtering the-cold reaction slurry fromnitrobenzene,=washing with very little nitrobenzene and then removingthe nitrobenzene and soda ash by steam distillation and subsequentfiltration and washing to freedom from alkali. 8-nitro-l,1'-dianthrimideis a bright red crystalline product appreciably soluble in nitrobenzeneand in high boiling solvents. It is soluble in cold sulfuric acid with ayellow-olive-green color. It is altered by hot concentrated sulfuricacid.- 'It is nearly insoluble in cold alcohol.

In this. example there may be used instead of a pure 8-nitro-lchloroanthraquinone aproduct whichisobtained by removing the 1,5 isomerfrom the'crude nitration mixture of anthraquinone alpha sulfonic acid byfiltration, by diluting the filtrate to a sulfuric acid concentration of80% and recovering a crude 8-nitroanthraquinone-l-sulfonic acid byfiltration and by chloriacid and sodiumchlorate at the boil.

nating the latter product with dilute hydrochloric EXAMPLE 2S-nitTo-LP-dMnthTimide I parts of '5-nitro-l-chloroanthraquinone (madefrom anthraquinone-5-nitro-1 sulfonic acid by boiling withdilutehydrochloric acid and sodium chlorate), 2 5 parts alpha aminoanthr'aquinone, 5 parts cupric chloride crystals and 48- parts soda ashare slurried in 400 parts of nitrobenzene. The mixture is heated to theboil allowing the water formed by the reaction to distill off. After ashort time the brown colored mass turns a deep red color which ischaracteristic of the 5-nitro-1,1'-dianthrimide. The re action is heldat the boil for 2-5 hours. On cooling the 5-nitro-I,1-dianthrimidecrystallizes out as a thick mass and can be isolated in sufilcientpurity by diluting, the slurry with 3-4 volumes'iof ethanolormethan'ol,invwhich the 5-nitro-l,ldianthrim-iderisinsoluble, filtering and.washing with alcohol to remove the mother liquor. The

soda ash is then-removed by slurryingthecake in dilute hydrochloricacid, filtering and washing product is obtained in this manner.

then removing the nitrobenzene and soda ash by steam distillation andsubsequent filtration and" washingtofreedom from alkali. v i

This 5-nitro-1,1"-dianthrimide i resembles? the S-nitro-LIT-dianthrimidein appearance. It: .alsodissolves .in concentratedsulfuric acid with ayellow-olive color. It is nearly insoluble incoldalcohol, but is solublein hot mononitrobenzene, but to a lesser degree than. is the8'-nitro-1,1'-dianthrimide. 1 '1 m' 1 1 .EXAMP'LE 3 1 Crude miitture ofX nitra and 5-nitro-1, 1"

- .dianthrimides V p as parts of. the crude mixture of B-nitroand5-nitro-1-chloroanthraquinone' '(obtained by diluting the crudenitration mixture of ,anthraquininealpha sulfonic acid without removalof the 1.5 isomer to asulfuric acid concentration, of 80 filtering theprecipitated mixture of nitrosulfonic acids and chlorinating it byboiling with dilute hydrochloric acidand sodium chlorate) 25 parts alphaamino anthraquinone, 5 parts cupric chlo-- ride crystals and parts sodaash are slurried in-400 parts of nitrobenzene.

brown colored mass turns a deep red color. .The reaction is held at theboil for 2-5 hours, On

cooling the nitro-1,1'.-dianthrimides= crystallize-- zene and thenremoving the nitrobenzene and ze'ne and in high boilingsolvents. It is[soluble'in cold sulfuric acid with a yellow-olive-green color.

The, mixtureis. heated to the boil, allowing the water formed bythereactionto distill off. After a short time the:

t is altered: hr hot: eoncentratedijsulfuric acid. tis; near y insolublein old alcohol.

I v Exmvrprs 4 8,4,4'etricmin0-L1Gdianthrimide NH O N111 ll llnal'cool-ing 51 parts (which isin excess) of the nit-rating acid (449%nitric acid, 45% sulfuric acid, I

and 6%wateri during one half hour. When the nitrating acid is all inthe. temperature isallowed to'rise25-27" C. and kept-th'ere three hourslonger under'stirring. The purplish-bluecharge is then poured into 2000parts of cold Water, stirred well and heated-to" 90" C; to hydrolyze theboric acid esters. Upon heating. the slurry first becomes purplish-redthen brick-red, and eventually orange-brown in color. It isthen filteredhot an I washed? acid free.

The filter cake is. well dispersedby slurrying it in 2000 parts coldwater and reduced by adding-28" parts of 50% sodium hydroxide solutionand 85 parts of 32% sodium sulfhydrate solution. The slurry is heated to50 C; at which point the product for the most part dissolves to give agreenblack solution. After one-half hour atthis temperature, thetemperature israised to the boil in about 30 minutes. A test at thispoint by spotting a drop on filterpaper'alongside a drop offerroussulfate solution will show the presence of excess sodium sulfide by ablack line atthe point of contact of the outrun of the spots. Thereduction product precipitates. Afterholding for one-half hour atthe-boilfadding more sodium sulfide if necessarythe slurry is filteredhot and Washed with-hot water until the filtrate, which at first is darkpurple,- becomes water-white. The filter cakeis dried at 80-90 C.,yielding a slightly bronzy-black powder in practically theoreticalyield. This product is mainly 8,4,4"-triamino- 1,I "-dianthrimide. It issoluble in concentrated sulfuric acid with-a blue color. Itcontains'three active amino groups and may or may not contain alsoahyd-roxyl group in position 25 or 2.

EXAMPLE 5 5.4,4.'-.-tridmino- 1,1' dianthrimide I NHL N HE' O NH: Cl

longer under stirring. The

the 5-nitro-1,l-dianthrimide of Example 2 are then stirred in until acomplete blue solution is obtained. The charge is cooled to 10-15" C.and at this temperature there are added under external cooling 51 parts(which is in excess) of nitrating acid (49% nitric acid, 45% sulfuricacid, and 6% water) during one-half hour. When the nitrating acid is allin the temperature is allowed to rise to -27 C. and kept there threehours longer under stirring, The purplish-blue charge is then pouredinto 2000 parts of cold water, stirred well and heated to 90 C. tohydrolyze the boric acid esters. Upon heating the slurry first becomespurplish-red, then brick-red and eventually orange-brown in color. It isthen filtered hot andwashed acid free.

The filter cake is well dispersed by slurrying it.

in 2000 parts of cold, water and reduced by adding 28 parts of 50%.sodium hydroxide solution and 85 parts of 32% sodium sulfhydratesolution. They slurryis heated to 50 C. at which point the product forthe most part dissolves as a green-black solution. After one-half hourat this temperature, the temperature is raised to the boil in aboutminutes. A test at this point by spotting a drop on filter paperalongside a drop'of ferrous sulfate solution will show the presence ofexcess sodium sulfide by ablack line at the point of contactof theoutrun of the spots. :Thereduction product precipitates. After holdingfor one-half hour at the boil, addin more sodium sulfide if necessary,the slurryis-filtered hot and washed with hotwater until the filtrate,which at first is dark purple, becomes water-white. The filter cake isdried at 8 090 C., yielding bronz'y-black powder in practicallytheoretical yield. This produce is 5,4,4'-triamino-1,,1" dianthrimide.It is soluble in concentrated sulfuric acid with a blue color. Itcontains three active amino groups and may or may not contain also ahydroxyl' group in position 2 or-2'.

EXAMPLE 6 Crude mixture 0ft, and8,4,4'-triamino-1,1' dianthrzmz'des Ithen stirred in until a complete bluesolution is obtained. The chargeis'cooled' tom-1 5 C. and at this: temperature, using external cooling,there are added 51 parts (which is in excess) of nitrating acid (49%nitric'acid', sulfuric acid; and 6%. water) during one-half hour. Whenthe nitrating acid is all in the temperature is allowed to rise to 25-27C. and kept there three hours purplish-blue charge is then poured into2000 parts of cold water, stirred well and heated to 90 C. to hydrolyzethe boric acid esters. Upon heating the slurry first becomespurplish-red, then brick red and eventually orange-brown in color. It isthen filtered hot and washed acid free.

The filter cake is well dispersed by slurrying it in 2000 parts coldwater and reduced by adding 28 parts of. 50% sodium hydroxide solutionand parts of 32% sodium sulfhydrate solution. The slurry is heated to 50C. at which point the product for the most part dissolves as agreenblack solution. After one-half hour at this temperature thetemperature is then raised to the boilin-;ab.out 30-minutes.- Atestatthis point by a slightlyspotting a drop on filter paper alongside a dropof ierrous sulfate solution will show the presence of excess sodiumsulfide by a black line at the; point of contact of the outrun of thespots. The reduction product precipitates. After holding for one-halfhour ,atthe boil, adding more sodium sulfide if necessarmthe slurryis-filtered hot and washed with hot water until the filtrate, which atfirst is dark purple becomes water-white. The filter cake is dried at80-90 C2,, yielding a slightly bronzy-black powder in practicallytheoretical yield. This product ismainly a mixture of 5 and8,4,4'-triamino'-1,1'-dianthrimides. It is soluble in concentratedsulfuric acid with a blue color. It contains-three active amino groupsand may or may not contain also hydroxyl groups.

ExAMrLE'l 1'',4',1',1,4,1"',8,1'"' pentanthrimide 50.4 parts of the8,f1,4'-triamino-1,1'. -.dian: thrimide of Example 4, in well pulverizedform, 78 parts of 1-chloroanthraquinone,,1l42 parts nitrobenzene, 87parts sodium'carbonate, 5 parts copper powder and '5 parts iodinecrystals are refluxed at approximately 210C, for Iourhours,

allowing the water of reaction to distill oil. The reaction mass becomesa'pulfple-black slurry givinga purple gray outrun whfin. S tted uponfilter paper. After cool'ng to room. temperature the slurry is filtered,washedwith 100 parts nitrobenzene and steam stripped to remove theresidual nitrobenzene'and to dissolve out the sodium carbonate. Theslurry, after filtering, is dried at 90% C. A yield of 90% or better canbe obtained. The product is a; black colored pow: der' s lubIe inconcentrated sulfuric acid with a yellow-olive color. It is insolublecold in nearly all organic solvents, but is slightly soluble in hothigh-boiling solve 7 ts. Analysis and chemical re;w

so. Y

"150.4 parts of the 5,4,4 -triamino-1, 1f -dianthrilamentsample 5', wellpulverized form, '78 parts; of",l-chloroanthraquinone, 1142 parts'nitrobenze' 'e, S'Z'p'arts sodium carbonate, 5 parts copper powder and5. parts iodine crystals are refiflfiiiedatpproximately 210 C.for fourhours answmgtri 'waterof reaction to distill off. The reaction inassbecomes a; purple-black slurry giving a purple-gray outrunwhen'spottedfupon filter paper. After, cooling to room temperature,the'sliirry filteifed, washed with 100 parts nitrob'enzeneandstamstipped to remove the residualnitrbbrizn' and to dissolve out thesoarbonatef' rnesiu'n-y, after filtering, is ur dfat, CLQJY-yieId or9o%or better can be obtained; lfIfhe roduct a black colored.powdeirfsolubleliiiIconcentrated sulfuric acid with a yellowoliveTcolon. ,It is insoluble cold in nearly all t)ig'itili'l.(i's'blvehts, but is Slightly soluble in hot high-boilingsolvfents;Analysis and chemical reactions show it' to 'be a trianthraquinonylderivatiVe 541,4 -t'1'i ainino 1,1" -dianthrimide.

obtained. The'product is a black colored powder,

soluble in concentrated-sulfuric acid with a yellow-olive color. It is,insoluble cold inqnearly all organic solvents, but is slightly solublein hot high-boiling solvents. Analysis and chemical reactions show it tobe a trianthraquinonyl derivative of the triamino-l,1'-dianthrimidesEXAMPLE Carbazole from the pentanthrzmide of Eaample 7 50.5 parts of thepent anthrimide of Example 7 in finely pulverized form is well mixedwith 25 parts (evenmore may be used if desired) sodium carbonate.Meanwhile 300 parts of pulverized anhydrous aluminum chloride aredissolved in 400 parts of commercial quality trichlorobenzene at 180 C.The"pentanthrimide-sodium carbonate mix is then'slowly added in aboutone-half hour at 180-200 C. under good stirring. The reaction issomewhatexothermic and may become vigorousafter about: two-thirds "ofthesoda'ashj mix is, in.f,' When; the latter hasfall been added'thetemperature is raised'to 200 C;', and' the charge becomes much thicker."It must notbe heated long at this pointybecause' to doso willdullandweakenth'e dyes'tufi. Thecharge is-drownedjirr a 'largejvolumejof water,filtered fronrexcess trichlorob'enzene and washed; to free from excessaluminum salts: V '1 Thefilter cake isput into a steam stripper; madestrongly alkaline withcaustic andstripped to free from'trichlorobenzene' and to breakup any aluminum chloride complex; whichmay he pres ent'. The slurry is then filtered, washed" neutral and driedat 905C: 'l'hegyi'el'dis practicallyquane titative; The."'polycarbazole" which. is obtained may be acid pasted; from 10. partsofjc'oncem trated" sulfuric acid at'temperatures ranging fromroomtemperature to190*"C.'without materially: afiectingtheshade:of'thedyestuff. The product sd'obtaiHed is black, giving with alkaline sodiumhydrosulfite abrown coloredvat from which cotton isdyeda very fast anddesirable greenish-olive drab shade of great intensity. The dyestufi is.only slightly soluble in most high-boilingsolvents, but issoluble inconcentrated sulfuric acid with; a brownish-purple colocfromwhich it isprecipitated on pouring into water as blackish-olive fiocs.

In this example the usages of both trichlorobenzene and aluminumchloride maybe. varied widely; Instead of; or together with trichloro-65 benzene other diluents; such as organic nitriles, acid halides,tertiary'cyclic bases'such a's'pyridine or dimethylaniline may beused.Thealuminum' chloride maybe used also in. the form of its compounds withsulfur dioxide-or withv sodiumchloride. However,- the activity of thedifferent ring'closing-agents varies to theefiect that a diff erent'numberof carbazole rings mightjbe' closed which results indyestuffsofsomewhat difierent shadesand properties,

C'drbjazoles o; the peritantlirimideiof Example 8 50.5 parts of thepentanthrimide of Example 8 in finely pulverized form are well mixedwith 25 parts (even more may be used if desired) sodium 1 carbonate.'Mea'nwhile300 parts of pulverized anhydrous aluminum: chloride aredissolved in 400 parts of commercial quality trichlorobenzene at 180 C.Thepentanthrimide-sodium carbonate mix is then slowly added in aboutone-half hour so at 180-200 0 under good stirring. The reacchargebecomes much thicker.

4 aluminum salts.

(ill

tion is somewhat exothermic and may become vigorous after. abouttwo-thirds of the soda ash mix is in. When the latter has all been addedthe temperature is raised to 200 (3., and the It must not be heated longat this point because to do so will dull and WeakenLthe dyestuff. Thecharge is drowned in a large volume of water, filtered from excesstrichlorobenzene andi washed; to free from excess 56 vat-fromwhichcottonis'dyedi-avery fastand desirable greenish olive drab shade ofgreatintensity: The" dyestuff isonlyrslightl-y' solubleinmost high'boilingsolventsi but is soluble 'ir'i} con-- a -brownish-purplecen-trated sulfuric acid w-it 60 color from which-it precipitated onpoui ing into- Thisdyes-tuif dyes similar shadesza-nd' has*similarproperties 'to the dyes tuifoi lil'xample 10;.

"i mean V Garbazole mixture from: tha'mnmnth rim'ide- 1 ;mi;ctureoifEaramz a9f-'; Y e 50.5: parts of-the pentanthrimide mixture ofExampleai'rrfi'nely pulverizedfbnnarewelhmixed 0 with ZS-parts' (eyenmoretm'aybf usediif desired) sodiumcarbonate.- Meanwhile 3oupartsfofpillverized; anhydrous: aluminum chloriderare dis;-

solved' in flGQ- parts off'conjmercial quality t-richlorobenzeneat 180(-3: The; pentanthrijmide sodium carbonate mix is th'en slowly addedinabout one-half hour at ISO-200 C. The pentanthrimide sodium carbonatemix is then slowly H added in about one-half hour at 180-200 C. undergood stirring. The reaction is somewhat exothermic and may becomevigorous after about 5 two-thirds of the soda ash mix is in. When the Vlatter has all beenadded the temperature is raised to 200 C'., and thecharge becomes much 0 thicker. It must not be heated long at this pointwhere one X Stands fo the group because to do so will dull and weakenthe dyel0 0 stuff. The charge is drowned in a large volume of water,filtered from excess trichlorobenzene and washed free from excessaluminum salts.

The filter cake is put into a steam stripper made strongly alkaline withcaustic and steam stripped Y to free from trichloroloenzene and to breakup any I NH aluminum chloride complex which may be present. The slurryis then filtered, washed neutral and the other X stands for hydrogen.and dried at 90 C. The yield is practically quan- A Vat dyesmfi havingthe formula; titative. The polycarbazole which is obtained may be acidpasted from 10-20 parts of concentrated sulfuric acid at temperaturesranging from room temperature to 190 C. without materially aifecting theshade of the dyestufi.

The product so obtained is black and gives with 5 alkaline sodiumhydrosulfite a brown colored vat from which cotton is dyed a very fastand desirable greenish-olive drab shade of great intensity. The dyestufiis only slightly soluble in most highboiling solvents, but is soluble inconcentrated 3 sulfuric acid with a brownish-purple color from which itis precipitated on pouring into water as blackish-olive flocs.

This dyestufi dyes similar shades and has simflag lfiope es t thedyestuffs of Examples 10 dyeing cotton a greenish-olive drab from abrownan vat.

I claim: 3. A vat dyestufi having the formula:

1. Vat dyestuffs being the carbazoles obtained by ring closure withaluminum chloride of pentanthrimides having the formula: q

1! A NH dyeing cotton a greenish-olive drab from a brown vat.

4. A vat dyestufi comprising a mixture of the 50 vat dyes of claims 2and 3. 0 GLEN M. SMYTI-I.

